Electrochemical reduction of CO₂ into various chemicals and fuels provides an attractive pathway for environmental and energy sustainability. It is now shown that a FeP nanoarray on Ti mesh (FeP NA/TM) acts as an efficient 3D catalyst electrode for the CO₂ reduction reaction to convert CO₂ into alcohols with high selectivity. In 0.5 m KHCO₃, such FeP NA/TM is capable of achieving a high Faradaic efficiency (FE ) up to 80.2 %, with a total FE of 94.3 % at −0.20 V vs. reversible hydrogen electrode. Density functional theory calculations reveal that the FeP(211) surface significantly promotes the adsorption and reduction of CO₂ toward CH₃OH owing to the synergistic effect of two adjacent Fe atoms, and the potential‐determining step is the hydrogenation process of *CO.